Treatment of wool-containing textile materials



Patented Jan. 23, 1951 TREATMENT OF WOOL-CONTAINING TEXTILE MATERIALSLinton A. Fluck, Jr., Pluckemin, N. J., and John E. Lynn, Old Greenwich,and Edward A. Schuman, Stamford, Conn., assignors to American CyanamidCompany, New York, N. Y., a corporation of Maine No Drawing. ApplicationAugust 12, 1948, Serial No. 43,963

Claims. (Cl. 8115.6)

g This invention relates to the treatment of textile materials, and moreparticularly to the treatment of wool and wool-containing fabric andother textile materials to impart improved properties thereto,specifically increased resistance to shrinking. Still more particularlythe invention is concerned with the improvement, in a method of reducingthe shrinking tendencies of a woolcontaining textile material with anaminoplast adapted to effect this result, which comprises treating thesaid textile material with an alkaline solution, more particularly anaqueous solution or an organic solvent (e. g., an alcoholic) solution ofa peroxy compound (e. g., hydrogen peroxide, an organic or inorganicperoxide, a perborate, a persulfate, etc.) prior to treatment with theaminoplast.

Many different methods and agents have been used or suggested for use inthe treatment of fabrics or other textiles composed of or containingwool in order to obviate or minimize their tendency to shrink onwashing. The proposed treata ing agentshave included halogens such aschlorine or bromine, solutions of sulfuryl chloride, hypochlorous acid,hypochlorites (e. g., sodium hypochlorite), alone or in the presence ofacidifying agents; alkalies (e. g., sodium or potassium hydroxide) ororganic bases, such agents being used under conditions such that onlythe surface structure of the wool fibers is altered; enzymes such aspapain; and reducing agents such as sodium hydrogen sulfide andmercaptoacetic (thioglycolic) acid. Another proposed shrinkproofingprocess has involved treating the wool-containing textile with anaqueous solution of a heat-curable resin, which is thereafter cured insitu, and then with a chlorine solution. Still another suggested processhas involved first treating the woolen fabric with an alcoholic causticsolution in such a manner that there is no intrinsic damage to thefibers and no harmful effect on the hand of the fabric. In the secondstep of the process the -woolen fabric is impregnated with an aqueoussolution or dispersion of a heat-curable aminoaldehyde (e. g.,urea-formaldehyde, melamineformaldehyde, etc.) resin-forming material orprecondensate, after which the impregnated fabric is heated toinsolubilize the impregnant. (For a more complete description of thislast-men-' 2 It was also suggested prior to our invention (see BritishPatent No. 553,923) that wool-comtaining textile materials be treatedwith an aqueous alkaline solution (pH of 8 to 12) of a substance capableof evolving oxygen (e. g., hydrogen peroxide, sodium peroxide, apersulfate, etc.) in order to reduce the tendency of the textile to feltand shrink. This treatment may be applied to the textile either beforeor after it has been treated with a sulfur-containing reducing agent, e.g., sulfur dioxide, a sulflte, a bisulflte, a hydrosulfite, etc. (seeBritish Patent No. 579,584). Another proposed shrinkprooflng treatment(see British Patent No. 564,958) has involved subjecting thewool-containing textile material to a mild chlorinating or brominatingtreatment controlled at a pH of 4 and then to treatment with an aqueousalkaline solution of hydrogen peroxide. Still another proposed method(see British Patent No. 569,730) of .shrlnkproofing wool-containingtextiles has involved treating the textile with an aqueous solution of apermanganate, e. g., potassium permanganate, and subsequently witheither an aqueous solution or suspension of a nitrogen-chloro compound,e. g., nitrogen trichloride, monochloroamine, etc., or a dilute aqueoussolution of an alkaline hypoclorite or hypobromite.

A process which is now widely used to render woolen and wool-containingtextile materials resistant to shrinkage involves treating the textilewith an aqueous solution or dispersion of an alkylated, specificallymethylated, methylol melamine, followed by heating the impregnatedmaterial to cure the alkylated methylol melamine to a substantiallywater-insoluble condition. This method is described, for example, inJohnstone, Jr., et a1. Reissue Patent No. 22,566, and the aminoplaststherein set forth are among those which are suitable for use inpracticing our invention.

The present invention is based on our discovery that a wool-containingtextile material including wool itself in fabric or other form can berendered resistant to felting and shrinking, with the use of a lesseramount of an aminoplast than previously was required, by a particularpreconditioning treatment of the textile prior to treatment with theaminoplast, which may be, for example, a methylated or other alkylatedmethylol melamine. Briefly, the preconditioning treatment comprisestreating the textile with an alkaline solution, preferably an aqueousalkaline solution, of a peroxy compound, preferably a water-solubleperoxy compound, prior to treatment greases 3 with the aminoplast. Itwas wholly unobvious and unexpected that pretreating the wool-containingtextile with an alkaline solution of a peroxv compound would makepossible a substantial reduction in the amount of methylated methylolmelamine or other aminoplast required to obtain a desired degree oishrinkage resistance together with other advantages described below,especially in view of our findings that the combination of treatmentsproduces results quite difl'erent from either treatment alone, asshownby examples which follow, and results which are not merely the sum ofthe individual treatments.

Other advantages flowing from the peroxy pretreatment, and which alsowere quite surprising and in no way could have been predicted, includethe greater uniformity in the results generally obtained with a givenaminoplast in treating a wider variety of textiles composed of orcontaining a proteinaceous material, specifically wool; and the abilityto use, with efl'ective results, other synthetic resins, moreparticularly aminoplastsother than those heretofore commonly employed inreducing the shrinkage tendencies of a wool-containing textile. stillanother advantage accruing from the preconditioning treatment employedin practicing our invention is the ability to render shrink-resistantwoolen textiles which heretofore could not be rendered resistant toshrinking to an appreciable O1 a commercially satisfactory degree bypreviously known methods.

The reasons why the treatment of a wool-containing textfle with analkaline solution of a peroxy compound prior to treatment with amethylated methylol melamine or other aminoplast is able to produce thevaluable and unobvious results above described are not understood. One

possible explanation, which is supported by our visual observations, isthat the treatment in some way alters the physical and/or chemicalcharac-.

teristics of the wool so that better wetting and/or penetration occursupon subsequent treatment with an aminoplast. This improvement inwettability and/or .penetrability is carried through any subsequentdyeing operation, as evidenced by the fact that no substantialdifferences in results are obtained when a dyeing step intervenesbetween the initial reconditioning treatment of the undyedwool-containing textile and the flnal treatment of the textile with anaminoplast.

In carrying our invention into efiect we first prepare a solution,preferably an aqueous alkaline solution, of a peroxy compound, moreparticularly such a compound which, in an aqueous medium, yieldshydrogen peroxide or, ultimately, oxygen. Illustrative examples ofperoxy compounds that may be employed are hydrogen peroxide and otherinorganic peroxides (e. g., sodium, potassium and other alkali-metalperoxides), the organic peroxides, (e. g., benzoyl peroxide, acetylperoxide, lauroyl peroxide, succinyl peroxide, tert.-butylhydroperoxide, etc.), the

various persalts including, for instance, the 8.1-

kali-metal (e. g., sodium, potassium, etc.), ammonium and otherperphosphates, persulfates, perborates, percarbonates, etc., thesepersalts in aqueous solution forming hydrogen peroxide. Organic peracids(e. g., peracetic acid, perbenzoic acid, etc.) and the alkali-metal andammonium salts of such acids also may be employed. Other percompoundswhich may be used include organic and organometallic salts of hydrogenperoxide, for instance tetramethyl, tetraethyl and other tetralkylammonium peroxides, triethyl tin peroxide, etc.

, soap, etc.

The concentration of peroxy compound in the alkaline solution may bevaried widely depending, for example, upon the particularwool-containlng textile employed, the particular peroxy compound used,the time and temperature of the treatment, etc. In general, however, theperoxy compound is used in an amount equivalent (oxidation equivalency)to at least about 0.05% by weight of hydrogen peroxide, based on theweight of the alkaline solution. Thus, when the peroxy compound ishydrogen peroxide, the alkaline pretreating solution ordinarily containsat least about 0.05%, more particularly at least about 0.1%, andpreferably at least about 0.2%, by weight of hydrogen peroxide; or, ifthe peroxy compound charged to the bath is other than hydrogen peroxide,then an amount thereof which is chemically equivalent as an oxidizingagent to at least about 0.05%, more particularly at least about 0.1%,and perferably at least about 0.2%, by weight of hydrogen peroxide isemployed. In most cases optimum results have been obtained when theconcentration of the peroxy compound in the alkaline solution isequivalent to a hydrogen peroxide concentration of at least 0.3% moreparticularly at least 0.5 or 0.6% by weight thereof. Higherconcentrations of peroxy compound, as for example concentrationsequivalent to hydrogen peroxide concentrations of the order of 2.5 or 3%or even 4 or 5% or more may be used if desired, but no particularadvantages appear to accrue therefrom. Due to its relatively low costand ease of handling the preferred peroxy compound is hydrogen peroxide,and generally it constitutes from about 0.3 to about 3%, moreparticularly from 0.5 to 2.5%, by weight of the aqueous alkalinesolution.

The preferred alkaline solution of the peroxy compound is an alkalinesolution of the peroxy compound in water. However, other alkalinesolutions in which the peroxy compound is soluble may be employed such,for example, as alkal'me solutions of the peroxy compound in an alcohol(e. g., a monohydric alcohol such, for instance as ethanol, propanol,butanol, etc), or in a mixture of water and an alcohol.

If the peroxy compound employed is of a kind which does not yield analkaline or a suificiently alkaline treating bath, then the bath is madealkaline or is brought to a desired degree of alkalinity, as for examplea pH of from about 8 to about 12, and more particularly to a pH ofbetween 9 and 11, by the addition of an alkaline material or a materialwhich reacts alkaline in aqueous solution. Any material capable ofrendering the treating solution alkaline or of bringingthe solution to adesired degree of alkalinity may be used, c. g., the sodium, potassiumand other alkali-metal hydroxides, acetates, carbon: ates andbicarbonates, ammonium hydroxide, amines (e. g., triethanolamine) borax,guanidlne carbonate, disodium phosphate, sodium silicates, Mixtures ofsubstances which react basic in aqueous solution may be used, ifdesired, for instance mixtures of such substances as those justmentioned byway of illustration.

The wool-containing textile to be preconditioned is treated with thealkaline solution of the peroxy compound in water or other solvent,preferably a volatile solvent, by any suitable method, for example byimmersing the textile in'the solution. The treatment may be effected bycontinuous, semi-continuous or batch methods, or by combinations of suchmethods. For instance, a wool-containing textile in skein, bolt or otherform may be immersed in the treating solution for a period suflicient toeffect the desired preconditioning treatment; or, the textile in, forexample, the form of a woven fabric may be continuously passed through abath of the solution at a rate such that it is immersed in the bath fora period suflicient to effect the desired results. If necessary,additional basic material may be added to the pretreating bath duringthe treatment in order to maintain the bath at a desired pH value.

The time of the treatment of the wool-containing textile with thepreconditioning solution may be varied considerably. Ordinarily,however, the contact time is at least 15 minutes, although in some caseseven shorter periods (for instance, periods of the order of or minutes)may be effective. Better results generally are obtained when the textileis in intimate contact with the preconditioning solution for a periodlonger than minutes, for example 30 minutes or longer. The time ofcontact may be 3 or 4 hours, or even as much as 1, 2 or more days insome cases, depending, for example, upon the particular wool-containingtextile which is being pretreated, the pH and temperature of thetreating solution, the kind and concentration of peroxy compoundtherein, and other influencing factors. In most cases, however, noparticular advantages appear to accrue. when the contact time is longerthan about 30 minutes, such a contact time usually being about aseffective as a contact time of 60 minutes or even of 3 hours when theother conditions including the peroxy compound (e. g., hydrogenperoxide), concentration thereof, alkaline material (e. g., sodiumsilicate), pH of the solution (e. g., about 10), temperature of thesolution, etc., are maintained substantially constant.

The temperature of the preconditioning solution also may be variedconsiderably but ordinarily it is within the range of about 110 F. toabout 160 F., the optimum temperature usually being about 125 F. In somecases. however, the solution temperature may be lower than 110 F., e.g., between 70 or 80 F. and 105 F., or it may be higher than 160 F., e.g., 165 F. or 175 F.

After treating the wool-containing textile with the alkaline solution(preferably an aqueous alkaline solution) of the peroxy compound, thetextile is usually water-washed and/or other wise treated to remove theexcess alkaline material. For example, the treated textile, aftersqueezing out the excess liquid, may be merely water-washed to removethe excess alkali; or, it may be water-washed and then rinsed in adilute acid solution (e. g., a 0.2 to 6 or 8% solution of a mineral acidsuch, for instance, as phosphoric acid or sulfuric acid, or a 0.2 to 10%solution of an organic acid such, for example, as formic acid or aceticacid), with or without further washing with water to remove the excessacid and water-soluble salts as desired or as conditions may require;or, the initial washing with water may be omitted, and merely. a diluteacid rinse followed, if desired or deemed necessary, by a water wash maybe used. The cycle of rinsing in dilute acid followed by water washingmay be repeated numerous times, if necessary, in order to remove theexcess alkaline material from the treated textile.

The preconditioning treatment herein described is applicable to bothundyed and dyed wool-containing textiles. When applied to dyedwool-containing textiles there is usually some loss of dyestufi, butwhether or not this occurs ated trimethylol melamine.

depends, of course, upon the resistance of the particular dyestufi tothe alkaline solution of the peroxy compound.

The preconditioned textile may be dyed by any of the methodsconventionally used in dyeing wool or w001-c0ntaining textiles withoutdetracting from the benefits of the peroxy pretreatment. For instance,wool in yarn, skein, fabric or other form may be dyed by top-chrome,meta-chrome or bottom-chrome dyeing methods. Typical of such dyeingprocesses are those briefly described below:

Top-chrome dyeing.-The dyestuff is applied first to the cloth in aboiling bath. The bath is cooled, a chrome salt (usually sodium orpotassium dichromate) added, the bath brought to the boiling point, andthen boiled for from 30 to 45 minutes.

Meta-chrome dyeing.--The chrome salt and dyestufi are applied to thewool in the same bath. Dyeing is started cold and finished at the boil.

Bottom-chrome dyeing.--Wool cloth is first boiled with a chromate in anacidified bath, the chrome color going onto the wool to give a darkgreen shade. The cloth is then boiled in a bath containing the dyestufi.The finished cloth may be any shade. Or, the wool may be dyed with ametallized dyestufi or an acid dyestufi such as are commonly used indyeing wool and in accordance with conventional practice. The wool alsomay be dyed with a v'at dye.

The final operation in carrying our invention into effect is thetreatment of the preconditioned, dyed or undyed, wool-containing textilewith a heat-curable aminoplast adapted to render the textile resistantto shrinking when the said aminoplast has been cured under heat to asubstantially water-insoluble condition. The preferred heat-curableaminoplasts, more particularly heat-curable or -convertibleamidogen-aldehyde (e. g., amidogen-formaldehyde) reaction prodnets arethose which are at least partly soluble in water. For example, theheat-curable aminoplast may be a substantially monomeric reactionproduct or a relatively low molecular weight intermediate reactionproduct of an aldehyde, specifically formaldehyde, with an amidogencompound containing a plurality of -NH2 groups, for instance urea,melamine, mixtures of urea and melamine, etc. Alkylated (e. g.,methylated, ethylated, propylated, butylated, etc.) reaction products ofan amidogen compound and an aldehyde, e. g., formaldehyde, may beemployed, for instance a 'methanolor other alkanol-reactedurea-formaldehyde, melamineforinalclehyde, etc., reaction product. Weprefer to use an alkylated, specifically methylated, methylol melamine,more particularly methyl- Such products are more fully described in, forexample, the aforementioned Johnstone, Jr., et a1. Reissue Patent No.22,566.

The heat-curable aminoplast may be applied to the undyed or dyedwool-containing textile material in various ways. For example, if theheat-curable aminoplast is applied in the form of an aqueous liquidcomposition (e. g., as a true solution or a colloidal dispersion)containing the same, the dry or substantially dry textile to be treatedmay be immersed in the aqueous composition and then passed throughpressure rolls, mangles or centrifugal extractors to secure uniformimpregnation and a controlled removal of the excess material. The woolenfabric or other wool-containing textile, however, also may beimpregnated by other methods, e. g., by spraying.

The liquid composition (e. g., an aqueous liquid'composition) containingthe heat-curable aminoplast in dissolved or dispersed state is dilutedwith a suitable solvent (e. g., water), if necessary, to yield afinishing composition hav-- ing the concentration of solids desired fortextile application. Thus, the concentration of solids in the liquidcomposition may be, for instance, from about 1 to about 20 or 25% byweight of the composition depending, for example, upon the method ofexpression of the wet, impregnated textile. Ordinarily, however, theheat-curable aminoplast constitutes from about 3 or 4% to about 10 or15% by weight of the liquid (e. g., aqueous) finishing composition. Thesolvent or dispersion medium for the heatcurable aminoplast may bevaried depending, for example, upon the characteristics of theaminoplast, but in the case of the preferred aminoplasts it is usuallywater; or it may be, for instance, a mixture of water and an alcohol, e.g., ethyl alcohol.

In order to speed up the curing of the heatcurable aminoplast or todecrease the heating time various catalysts may be added, if desired, tothe finishing composition, e. g., oxalic acid, acetic acid, phosphoricacid, diammonium hydrogen phosphate, diammonium ethyl phosphate,diammonium phthalate, ammonium chloride, ammonium silocofluoride, zincchloride and others which are known to be catalysts for ouringheat-curable aminoplasts, e. g., modified and unmodifiedmelamine-formaldehyde reaction products including the alkylated methylolmelamines. The amount of catalyst may be varied as desired or asconditions may require, but ordinarily it is employed in an amountcorresponding to from 0.5 to 5% by weight of the heat-curableaminoplast.

The pick-up of the liquid (e. g., aqueous) finishing composition by thewool-containing textile material should be adjusted so that the finishedtextile contains an amount of cured aminoplast sufiicient to impartshrink-resistant characteristics thereto which at least are adequate tomeet the minimum commercial requirements. This will vary somewhatdepending, for instance, upon' the particular wool-containing textile,being treated, the particular preconditioning treatment which has beengiven to it, the particular aminoplast employed, the particularproperties desired in the finished textile, etc. Ordinarily, however,the pick-up is adjusted so that the amount of aminoplast in the finishedtextile is not more than about (usually only about /2 or less) as muchby weight as that required to obtain the same shrinkproofingcharacteristics in the absence of the preconditioning treatment. For'example, the pick-up of the liquid finishing composition by thewool-containing textile material may beadjusted so that the finishedtextile contains from about 1 or 2% to about 6 or 8%, more particularlyfrom about 3% to about 5%, by weight of the dry textile, of the curedaminoplast. In some cases, as for instance in the case of those woolenor wool-containing textiles which normally are not amenable to treatmentwith an aminoplast alone to yield a commercially satisfactoryshrinkproofed textile, the pick-up of the liquid finishing compositionmay be adjusted so that the finished textile contains as much as about10% or even about or more, by weight of the dry textile, of the curedaminoplast. The amount of the aqueous or other liquid finishingcomposition picked up by the textile, that is, the so-called wetpick-up,"

8 may bevaried as desired or as conditions may require and may range,for example, from about 30 or 40% up to about or more by weight of thedry textile depending, for example, up n the particular textile treated,method and conditions of treatment, concentration of solids in theimpregnating bath, amount of solids and properties desired in thefinished textile, etc. When the woolen fabric or other wool-containingtextile material is impregnated with 100%, by weight 01' the drytextile, of the textile-finishing composition, the impregnated textilewill contain, after drying and curing of the heatcurable aminoplast,nearly the same percentage of cured aminoplast as the percentage ofheatcurable aminoplast which is present in the textile-finishingcomposition.

The wet, impregnated woolen fabric or other wool-containing textilematerial is then dried and cured. The drying and curing temperatures maybe varied considerably, but ordinarily temperatures within the range ofabout F. to about 400 F. are employed. The impregnated textile may beair dried or it may be dried under heat, e. g., at a temperature of theorder of about 160 F. to 212 F. to remove all or most of the water,after which the dried material is heated at a temperature within therange of about 250 F. to about 400 F. to convert or cure theheat-curable aminoplast to a substantially water-insoluble condition.

The drying and curing operation is flexible and may be varied to suitthe available equipment. Continuous methods are preferred. However,drying and curing also may be eilected by framing the impregnated fabricto width, as on a pin tenter, drying the framed fabric, batching it upona shell and then allowing it to stand hot for a period sufiicient toconvert the solid impregnant in situ to a water-insoluble condition. Insome cases drying and curing for 2 or 3 hours at 200 .1. may berequired. Heating the dried fabric at higher temperatures ranging from afew seconds to a few minutes at higher temperatures of the order of 250F. to 400 F. may be employed, the shorter periods being used at thehigher temperatures.

After the woolen fabric or other wool-containing textile material hasbeen treated as above described, it may be given a mild soapingtreatment to render it softer and more pliable. It then may be given theusual finishing treatments such as decatizing, brushing, shearing,pressing, etc. Our process may be applied to wool and wool-containingtextile materials, e. g., unwoven wool, yarns, worsteds, fiannels,shirting, felts, knit or woven goods and others, and these maybecomposed. of all wool o partly of wool and partly of another fibrousmaterial, e. g., cotton, silk, any of the various rayons, any of thevarious other synthetic fibers including nylon, polyacrylonitrilefibers, fibers produced from casein, soya, beans, etc.

In order that those skilled in the art better may understand how thepresent invention may be carried into effect the following examples aregiven by way of illustration and not by way of limitation. All parts andpercentages are by weight.

EXAMPLE 1 The textile material used in this example was undyed women'swear flannel, 100% all wool, weighing 8 ounces per square yard. Piecesof this ufianneLQinches by 23 inches insizeandwhich 30 minutes in anaqueous alkaline solution containing 0.6% by weight thereof of hydrogenperoxide and which had been rendered alkaline to a pH of about withsodium silicate. The solution was maintained at a temperature of about,

125 F. during the treating period. The treated 10 flannel was removedfrom the bath, rinsed thoroughly in water, squeezed through a padder andthen dried on a frame, while holding it to its original size of 9 inchesby 23 inches, for 10 minutes at 240 F.

13. Another sample of the flannel was impregnated by immersing it for atleast about 1 minute in an aqueous solution containing about 5% l byweight of methylated methylol melamine, more particularly methylatedtrimethylol melamine. The solution also contained, by weight, 0.155% ofa curing catalyst, specifically diammonium hydrogen phosphate, and 0.03%of a wetting agent, specifically dioctyl sodium sulfosuccinate. The wetflannel was then squeezed through a padder to yield an impregnated clothin which the wet pick-up was about 100% by weight of the dry flannel,after which the sample was framed to size as in A, and then heated for 9minutes at 290 F. to dry the fabric and to cure 10 shrinkage valuesgiven in other examples were determined in a similar manner.

Table I WARP SHRINKAGE IN PER CENT No. of Machine washings Untreatedflannel 22. 0 Treated flannel of A 13. 9 Treated fianncloill 7.2 10.011.9 Treated fiannelofC 6.3 5.0 0.1 Treated flannel ofD 4.4 6.1 6.1

EXAMPLE 2 This example illustrates the results obtained when the women'swear flannel used in Example 1 is treated as therein described butvarying the concentration of hydrogen peroxide in the pre- 0conditioning bath, the period of time the flannel is immersed in thisbath, and the manner of washing after the peroxide pretreatment. Thefinishing treatment with a 5% aqueous solution of a methylated methylolmelamine was the same as described under B of Example 1. The results areshown in Table II, together with warp shrinkage data on the untreatedflannel and on samples of flannel which had been treated with 5% and 10%aqueous solutions of methylated methylol melamine as described under Band C of Example 1.

Table II Warp Shrinkage Time of Acetic Acid Methylated Test No. H O:Treatgzgj figf fl No. oiMachlne washings ment ment Applied Pageant HoursPer canto Perzgegt Per cent Per cent 0.6 ,5 o 16: a 0 6 7. 2 10.0 11. 90 10 5. 3 5. 0 5. 1 0.6 3 5 6. 7 6. 9 7. 8 0. 6 1% 5 5. 0 5. 8 6. 4 0.634 5 4. 2 5. 0 6. l 0. 6 $6 5 4. 4 4. 7 5. 6 0v 6 M 5 5. 8 6. 7 6. 90.15 56 5 5. 8 6. 7 6. 4 0.3 M 5 6. 9 8. 0 8. 3 0.3 5 4. 2 5. 0 5. 8 1.236 5 6. 7 0. l 2. 4 5 6. 9 6. 0

the methylated methylol melamine to a substantially water-insolublecondition.

C. Same as described under B with the exception that the flannel wasimmersed in an aqueous solution containing about 10% of methylatedmethylol melamine (more particularly methylated trimethylol melamine),0.31% of diammonium hydrogen phosphate and 0.03% of dioctyl sodiumsulfosuccinate.

D. A sample of the flannel was preconditioned 60 as described under A,followed by treatment as described under B.

After cooling to room temperature each of the samples of A, B, C and Dwas removed from the frame and given 10 or more washings (soapings) of10 minutes each at 100 F. in accordance with Federal SpecificationsCCC-T-l91a. After steam pressing and conditioning for about 16 hours atF. and 65% relative humidity, the samples were measured for shrinkage ininches per yard, 7

which values were then changed to percentages. The warp shrinkage in percent of each of the treated samples, together with that of the untreatedsample (control sample which had been similarly washed), is shown inTable 1, other In Table II the word No under the fourth column headingmeans that the peroxide pretreated cloth was not given an acetic acidrinse but was merely rinsed in cold water and dried as described under Aof Example 1. The word Yes" under this same column heading means thatthe peroxide pretreated cloth was first rinsed in water, then in adilute acetic acid solution containing about 5% by weight of aceticacid, and finally with water to remove the acid. The same meanings applyto these words where they appear in other tables herein under the columnheading Acetic acid rinse after H202 treatment."

EXAMPLE 3 The textile material used in this example was a Neolan dyed,100% all wool flannel which weighed 8 ounces per square yard. It istypical of woolen fabrics which are less amenable to treatment with amethylated methylol melamine alone to render them adequately resistantto shrinking than the flannel used in Examples 1 and 2. The pretreatingbath was an aqueous alkaline solution containing 0.6% by "weight thereofof hydrogen eroxide and rendered alkaline to apI-I of about 10 withsodium silicate.

v i like the flannel used in Example 8 it is not readily amendable totreatment with a methylated methylol melamine alone to render itshrinkageresistant. Because of the residual sulfuric acid 5 in thiscarbonized flannel, about three times the normal amount of sodiumsilicate was required to provide and keep the pretreating bath at a pHof about 10 during the peroxide pretreatment. The results are shown inTable IV, together with warp shrinkage data on the untreated flannel andon a sample of the flannel which had been treated with a 10% aqueoussolution of methylated The alkaline hydrogen peroxide pretreatment TableIII Warp Shrinkage Tam Thu Acetic Acid :23 Tensile mo, Treatg g- 33%methylol No. ollhchinewashinga ggg mt ment m Plus 10 no so m Per Percent Hoar: Puneat mu cent on: Pound: o o as 49.0 so s :1. o o 10 10. s20. s o. s 2 a s. s 1. 2 o. 2 72 0.6 a 5.6 M 1.5 75 0. G 3 5 5. 3 6i 77. 2 o o a Yes----- s 4. 2 a. e s. o

methylol melamine as described under C of Ex precondition the cloth andthereby obtain outstanding and unobviousshrinkage-controlcharacteristics upon subsequent treatment withthe 5% methylated methylolmelamine solution.

EXAMPLE4 Same as Example 3 with the exception that the textile materialwas a 100% all wool, 8-ounce flannel which had been carbonized in aparticular manner. The flannel was an undyed wool, but

, stripped the color fromthe yellow wool, but did ample 1.

Table IV 7 Warp Shrinkage T ml Acetic Acid gg?- T633116 n.0, im M thylolNo ofllachinewashings st'engm ment Treat" Melamine I (warp ment AppliedPlus m m m Filling) Per I Per Per Per cent Harm Per cent can! out outPound: o 0 ads 4m 76 0 10 0.4 14.7 as a No a 1.1 2.5 a1 o c s; Yes 5 a au s. o 19 0.6 ire-5..."... s 0.1 1.5 so 75 not detract from the abilityof the peroxide to EXAMPLE 5 and before the finishing treatment with the5% aqueous methylated methylol melamine solution.

Table V Warp Shrinkage Total same m ll Hi0: m i- Hi0 M lhiiglglg lgleNo. 0! Washing; (warp merit Applied Falling; 10 so so g Per Per Per Percent Hours Per em: out real coat Pound: 0 0 43. 0 74 0 l0 7. 2 11. 4 12.8 0. 6 3 6 6. 8 6. 1 6. 4 0. 8 3 6 4. 4 4. 7 5. 0 0. 6 i2 5 5. 3 5. I 5.3 76 0. 0 6 8. 9 4. 4 4. 7 75 0. 6 3 6 8. 3 4. 2

Nora: After the peroxide pretr eatment the sample was top-chrome totreatment with th e aqueous methylated methylol melu n subsequenttreatment I no m t ylsl e dy d wool with the aqueous meth- 13 EXAMPLE 6In this example 100% all wool, women's wear flannel weighing 8 ouncesper square yard was treated as described briefly below, the details ofthe steps being the same as described in prior examples.

A. The wool was immersed for 30 minutes in an aqueous solution of sodiumsilicate in a concentration such as to give the solution a pH of about10. The solution was maintained at 125" F. during the treating period.The cloth was removed from the treating bath, rinsed in cold water anddried.

B. Same as A with the exception that the pretreating solution was anaqueous solution containing only 0.6% by weight thereof of hydrogenperoxide.

C. Same as A with the exception that the pretreating solution contained0.6% by weight thereof of hydrogen peroxide and was rendered alkalinewith sodium silicate to a pH of about 10.

D. The flannel, without any preconditioning treatment, wastreated with aaqueous solution of methylated methyloi melamine as described under B ofExample 1.

E. The wool was treated as described under A, supra, rinsed first inwater, then in a dilute aqueous solution ofacetic acid and again inwater, dried, and finally treated with a 5% aqueous solution ofmethylated methylol melamine as described under B of Example 1.

F. Same as E, supra, with the exception that the preconditioningtreatment was the same as described under B, supra.

G. Same as E, supra, with the exception that the preconditioningtreatment was the same as described under C, supra.

The treated flannels and a control sample (untreated flannel) weresubjected to washing in soap solution, more particularly flve washingcycles of 10 minutes each followed by drying, and then were washed for 1hour followed by drying. The data on shrinkage of the treated and washedThe same kind of flannel was treated as that employed in Example 6. Thetreatments were as follows:

A. The flannel, without any preconditioning treatment, was treated withan aqueous solution containing 10% of trimethylol melamine, 0.31% ofdiammonium hydro-gen phosphate and 0.03% of dioctyl sodiumsuifosuccinate.

B. The woolen goods was preconditioned by treatment as described under Aof Example 6, rinsed first in water, then in a dilute aqueous solutionof acetic. acid and again in water, dried, and finally. treated asdescribed under A of this example.

0. Same as B of this example with the exl4 caption that thepreconditioning treatment was the same as described under B of Example6.

D. Same as B of this example with the exception that the preconditioningtreatment was the same as described under 0 of Example 6.

The treated flannels and a control sample were washed as described underExample 6. The shrinkage data on the treated and washed samples areshown below:

Treatm t Bhr in gs in Per Cent None. 4 18. 6 A s. o R 8. 0 O 7. 8 D 4. 2

EXAMPLE 8 C. Same as B of this examplev with the exception that thepreconditioning treatment was the same as described under B of Example6.

D. Same as B of this example with the exception that the preconditioningtreatment was the same as described under C of Example 6.

The treated flannels and a control sample were washed as described underExample 6. The shrinkage data on the treated and washed samples areshown below:

Warp Treatment Shrinkage in Per Cent EXAMPLE 9 and thereby obtainimproved shrinkage resistance upon subsequent treatment with theheat-curable aminoplast.

The treated flannels and a control sample were washed as described underExample 6. The

shrinkage data on the treated and washed samples are shown below:

In this example a diiierent peroxy compound,

viz., sodium perborate, was employed. The fabric treated was a womenswear flannel such as was used in Example 1. The treatments were asfollows:

A. Same as B of Example 1, that is, the flannel D. The flannel waspreconditioned by immersing it in an aqueous alkaline solutioncontaining 1% by weight of sodium perborate, which bath differed fromthe solution of C of this example in that no sodium silicate was added.(The sodium perborate alone brought the bath to a pH of about 10.) Theflannel was allowed to remain in the bath for 30 minutes whilemaintaining the solution at 125 F. After rinsing with water and dryingas described under A of Example 1, the preconditioned flannel wastreated with a solution containing 5% by weight of methylated methylolmelamine as described under B of Example l.

The treated flannels and a control sample were washed as described underExample 6. The shrinkage data on t treated and washed samples are shownbelow.

Treatment ,a m s-"M #200306 EXAMPLE 11 The woolen material which wastreated in this example was the same as that used in Examples 6, 7 and8. The treatments were as follows:

A. Same as D of Example 1 with the exception that the hydrogen peroxidepreconditioning bath, which had been rendered, alkaline to a pH of about10 with sodium silicate, was maintained at about 150 F. during theperiod the flannel was immersed in the bath. The pretreating solutioncontained 0.6% by weight of hydrogen peroxide. The final treatment waswith a solution containing 5% by weight of aqueous methylated methylolmelamine as described more fully under B of Example 1.

i B. Same as A of this example with the excep- 16 tion that theper-conditioning solution contained 1.2% by weight 01' hydrogenperoxide.

0. Same as A of this example with the exception that thepretreating'solution contained 2.4% by weight oi hydrogen peroxide.

The treated flannels were washed as described under Example 6. Theshrinkage data on the treated and washed samples are shown below:

Warp

EXAMPLE 12 The woolen fabric which was treated in this example was a allwool, womens wear flannel weighing 8 ounces per square yard. Thetreatments were as follows:

A. Same as D of Example 1 with the exception that the hydrogen peroxidepreconditioning solution was rendered alkaline to a pH of about 10 withsodium carbonate instead of with sodium silicate as in Example l-D.

B. Same as D of Example 1 with the exception that the preconditioningbath was rendered alkaline to a pH of about 10 with guanidine carbonate:

C. Same as D of Example 1 with the exception that the hydrogen peroxidepretreating solution was brought to a pH of about 9 withtriethanolamine.

D. Same as D of Example 1 with the exception that the preconditioningbath was rendered alkaline to a pH of about 8 with sodium acetate.

E. Same as D of Example 1 with the exception that the peroxidepreconditioning solution was made alkaline to a pH of about 10 withsodium hydroxide.

F. Same as D of Example 1 with the exception that the peroxidepretreating solution was brought to a pH of about 8 with soap.

The treated goods and a control sample were washed as described underExample 6. The shrinkage data on the treated and washed The woolenfabric treated in this example was a womens wear flannel such as wasused in Example 1. The treatments were as follows:

A. The flannel, without any preconditioning treatment, was treated withan aqueous solution containing 5% of methylated dimethylol urea, 0.155%of diammonium hydrogen phosphate and 0.03% of dioctyl sodiumsulfosuccinate.

B. Same as A with the exception that the flannel was treated with anaqueous solution con taining 10% of methylated dimethylol urea, 0.31% oidiammonium hydrogen phosphate and 0.03% of dioctyl sodiumsulfosuccinate.

C. Same as A with the exception that the flannel was preconditioned bytreatment with Warp Shrinkage in Per Cent After 5 Treatment After 1 Hour01' igfif g Additional Each Washing EXAMPLE 14 Same as Example 13 withthe exception that instead of the aminoplast employed in B and D of thatexample there was used a 10% aqueous solution of a substantiallyunpolymerized reaction product of formaldehyde and urea in the ratio ofabout 1.33 moles of the former to 1 mole of the latter (B and D of thisexample); and instead of the aminoplast employed in C of Example 13there was used a aqueous solution of the same aminoplast just mentioned(C of this example). In each case the solution also contained 0.03% ofdioctyl sodium sulfo-- succinate, and diammonium hydrogen phosphate inan amount corresponding to about 3.1% by weight of the aminoplast in thesolution.

The shrinkage data on the treated samples after being washed are shownbelow:

Same as Example 13 with the exception that instead of the aminoplastemployed in B and D 01 that example there was used a aqueous solution ofa partial reaction product of urea and formaldehyde in the ratio of 1'mole of the former to from 2.0 to 2.1 moles of the latter; and insteadof the aminoplast employed in C of Example 13 there was used a 5%aqueous solution of the aminoplast just mentioned (0' of this example).In each case the solution also contained 0.03% of dloctyl sodiumsulfosuccinate and diammonium hydrogen phosphate in an amountcorresponding to about 3.1% by weight of the aminoplast in the solution.

The shrinkage data on the treated samples after being washed are shownbelow;

Warp Shrinkage in 1... Cent Treatment agai After 1 3 Hour of C i i"Additional nu 83 Each Washing EXAMPLE 16 Same as D of Example 1 with theexception that the flannel was immersed in an aqueous solutioncontaining 2 /2% by weight of methylated methylol melamine. The warpshrinkage in per cent of the treated flannel, after 5 washing cycles of10 minutes each followed byl hour's washing was 4.2.

EXAMPLE 17 Same as D of Example 15 with the exception that, instead ofdrying and curing the impregnated flannel by heating for 9 minutesat 290F.. the period. and temperature of heating were, in one case (A), 9minutes at 225 F. and, in another case (B), 15 minutes at 290 F. Theshrinkage data on the treated samples after being washed are shownbelow:

Treatment Aiter 5 Washing Cycles of 10 Minutes Each Plus One Hour!Additional Washing.

EXAMPLE 18 which was treated was a all wool, womens wear flannel such aswas used in Example 1. The treatments were as follows:

A. Same as D of Example 1 with the exception that the woolen fabric wasimmersed in the alkallnehydrogen peroxide pretreating bath at atemperature of 100 F. for 8 hours instead of at F. for 30 minutes as in1-D. The textileflnishing composition contained about 5% of methylatedtrimethylol melamine and the same kind and amount of curing catalyst andwetting agent as in 1-D.

B. Same as A of this example with the exception that the pretreatingbath was maintained at a temperature of about 80 F. for about 24 hours.

The treated flannels and a control sample were washed as described underExample 6. The

.shrinkage data on the treated and washed samples are shown below:

Aiter 5 Washing Cycles of 10 Minutes Each Followed by One Hour ofAdditional Washing.

It will be understood, of course, by those skilled in the artfthat ourinvention is not limited to the particular preconditioning compositions,heatcurable amlngplasts, curing catalyst and conditions of treating awool-containing textile with these compositions as has been given by wayof illustration in the above examples, since the pretreating solution,the final textile-finishing composition and the application conditionsmay be widely varied as will be apparent from the description in thisspecification prior to the examples. 7

The terms textile and textile material as used generally herein and inthe appended claims include within their meanings filaments, fibers,rovings, slivers, threads, yarns, twisted yarns,

etc., as such or in woven, felted or otherwise formed fabrics, sheets,cloths and the like.

In the copending application of Linton A. Fluck, Jr., John E. Lynn andEleanor L. McPhee, Serial No. 43,964, filed concurrently herewith, isdisclosed and claimed a process of reducing the shrinking tendencies ofa wool-containing textile material which comprises preconditioning thetextile material by first treating it with an alkaline solution of aperoxy compound as herein described, impregnating the preconditionedtextile with an impregnant comprising a colloidal solution of a curablecationic aminoplast (e. g., a curable, cationic product of reaction ofingredients comprising melamine and formaldeaminoplast, and advancingthe cure of the said aminoplast in situ, the amount of cured aminoplastin the said textile material being suflicient to render it resistant toshrinking.

2. A process as in claim 1 wherein the alkaline solution of the peroxycompound has a pH of at least 8.

3. A process as in claim 1 wherein the alkaline solution is an aqueousalkaline solution and the peroxy compound is a water-soluble peroxide.

4. A process of reducing the shrinking tendencies of a woolen fabricmaterial which comprises preconditioning the said fabric material byfirst treating it with an aqueous alkaline solution of hydrogen peroxideand thereafter removing the excess alkaline material, impregnating thepreconditioned fabric with an impregnant comprising a curable,non-cationic aminoplast which is a reaction product of ingredientscomprising melamine and formaldehyde, and advancing the cure of the saidaminoplast in situ, the amount of cured aminoplast in the said fabricmaterial being sufiicient to render it resistant to shrinking.

5. A process of reducing the shrinking tendencies of a dyed,wool-containing tetxile material which comprises preconditioning theunwith a curable, non-cationic aminoplast, and advancing the cure of thesaid aminoplast in situ to its ultimate form, the cured aminoplast beingsubstantially water-insoluble, and the amount of cured aminoplast in thesaid textile material being from about 1% to about 15% by weight of thedry, untreated textile material.

6. A process as in claim 5 wherein the aqueous alkalinesolution has a pHof between 8 and 12.

7. A process of reducing the shrinking tendencies of a dyed,wool-containing fabric material which comprises immersing the undvedfabric material in an aqueous alkaline solution of hydrogen peroxide andthereafter removing the excess alkaline material thereby to preconditionthe undyed fabric, dyeing the preconditioned fabric, impregnating thedyed fabric with an aqueous composition comprising a curable,non-cationic aminoplast which is a reaction product of ingredientscomprising melamine and formaldehyde, drying the wet, impregnated fabricmaterial and polymerizing the said curable aminoplast contained in theimpregnated fabric to its ultimate degree of polymerization, said dryingand polymerization being effected at a temperature not exceeding 400 F.,and the amount of polymerized aminoplast in the said fabric being from 1to 15% by weight of the dry, untreated fabric.

8. A process as in claim 7 wherein the hydrogen peroxide is employed ina concentration of at least 0.05% by weight of the aqueous alkalinesolution.

9. A process as in c aim 7 wherein the aqueous solution is renderedalkaline with sodium silicate to a pH of between 9 and 11.

10. A process of reducing the shrinking tendencies of a dyed, woolenfabric material which comprises immersing the woolen fabric material,prior to dyeing, for a period of at least 15 minutes in an aqueoussolution rendered alkal ne with sodium silicate to a pH of between 9 and11 and containing hydrogen peroxide in an amount corresponding to from0.05 to 5% by weight of the said solution, said solution beingmaintained at a temperature with n the range of F. to 160 F., thereafterremoving the excess sodium silicate from the thusly treated fabricmaterial thereby to precondition the undyed fabric, dyeing thepreconditioned fabric, impre nating the dyed fabric with an aqueoussolution of a noncat onic methylated methylol melamine, drying the wet,impregnated fabric and polymerizing the methylated methylol melaminecontained in the impregnated fabric to its ultimate degree ofpolymerization, said drying and polymerization being effected at atemperature withn the range of about 65 F. to about 300 F., and theamount of polymerized methylated methylol melamine contained in the saidfabric being from about 1% to about 15% by weight of the dry, untreatedfabric.

11. The method of producing a dyed woolcontaining textile material whichis resistant to shrinking, said method including, as essential steps,treating the undyed wool-containing textile dyed textile material byfirst treating it with an aqueous alkaline solution of a water-solubleperoxide, dyeing the preconditioned textile material, impregnating thedyed textile mater al material with an aqueous solution renderedalkaline to a pH of between 8 and 12 and containing hydrogen peroxide inan amount corresponding to from 0.1 to 3% by weight of the said solutionthereby to precondition the said textile material, dyeing thepreconditioned textile material, impregnating the dyed preconditionedtextile material with a curable, non-cationic product of partialreaction of ingredients comsistant to shrinking and constituting fromabout 1% to about 15% by weight of the dry untreated textile material.

12. The method of producing a dyed woolen fabric material which isresistant to shrinking, said method comprising treating the undyedwoolen fabric material with an aqueous solution rendered alkaline withsodium silicate to a pH of between 9 and 11 and containing hydrogenperoxide in an amount corresponding to from 0.2 to 2.5% by Weight of thesaid solution thereby to precondition the said fabric material, removingthe excess sodium silicate from the thusly treated material, dyeing theresulting material, impregnating the dyed material with an aqueoussolution of a non-cationic methylated methylol melamine, drying the wetimpregnated material, and thereafter heating the dried material at atemperature within the range of 250 F. to 400 F. to cure the methylatedmethylol melamine contained therein to a substantially water-insolublecondition, the amount of cured methylated methylol melamine with whichthe said fabric material is impregnated being sufiicient to render itresistant to shrinking, said cured methylated methylol melamineconstituting from about 2% to about by weight of the dry untreatedfabric material and being substantially less than that required toproduce the same degree of shrinkage resistance in the same woolenfabric material with the same methylated methylol melamine in theabsence of the aforesaid hydrogen peroxide preconditioning treatment.

13. The method of reducing the shrinking tendencies of a Woolen textilematerial which comprises immersing the said material in undyed state forfrom A to 3 hours in an aqueous solution rendered alkaline to a pH ofbetween 9 and 11 and containing hydrogen peroxide in an amountcorresponding to from 0.5 to 2.5% by weight of the said solution therebyto precondition the said textile material, said solution beingmaintained at a temperature of from 70 F. to 160 F.; removing the excessalkaline material from the preconditioned textile; impregnating thepreconditioned textile from which the excess alkaline material has beenremoved with an aqueous solution of a curable, non-cationic methylatedmethylol melamine, said solution containing from, about 3% to about 15%by weight of the said methylated methylol melamine and a curing catalysttherefor in an amount corresponding to from 0.5% to 5% by weight of themethylated methylol melamine; adjusting the pick-up of the said aqueoussolution by the said preconditioned textile so that the amount of curedmethylated methylol melamine in the finislrcitextile is from about 2% toabout 10% by weight of the dry untreated textile and not more than aboutthree-fourths as much by weight as that required to obtain the sameshrinkproofing characteristics in the absence of the aforedescribedpreconditioning treatment; drying the wet impregnated textile; andheating the dried textile at a temperature within the range of 250 F. to400 F. to cure the methylated methylol melamine contained therein to asubstantially water-insoluble condition.

14. The method of producing a wool-containing textile material which isresistant to shrinking, said method including, as essential steps, firsttreating the said textile material with an aqueous solution renderedalkaline to a pH of between 8 and 12 and containing hydrogen peroxide inan amount corresponding to from 0.1 to 3% by weight of the said solutionthereby to precondition the said textile material, impregnating thepreconditioned textile material with a curable, non-cationic aminoplast,and thereafter subjecting the thusly impregnated wool-containing textilematerial to an elevated temperature sufficient to cure the saidaminoplast contained therein to a substantially water-insolublecondition, the amount of cured aminoplast with which the said textilematerial is impre nated constituting from about 1% to about 15% byweight of the dry, untreated textile material.

15. A method as in claim 14 wherein the curable, non-cationic aminoplastis a curable, noncationic product of partial reaction of ingredientscomprising melamine and formaldehyde.

LINTON A. FLUCK, JR. JOHN E. LYNN. EDWARD A. SCHUMAN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,389,274 Schweitzer Aug. 30,1921 2,070,210. Mason Feb. 9, 1937 2,107,297 Kauffmann Feb. 8, 19382,238,949 Schlack Apr. 22, 1941 2,329,622 Johnstone Sept. 14, 19432,329,651 Powers Sept. 14, 1943 2,395,724 Cowley Feb. 26, 1946 2,395,791Pfeffer Feb. 26, 1946 2,467,233 Rust Apr. 12, 1949 FOREIGN PATENTSNumber Country Date 408,985 Great Britain Apr. 20, 1934 553,923 GreatBritain 1943 certificate of Correction Patent No. 2,539,365 January 23,1951 LINTON A. FLUCK, JR, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows:

Column 2, line 27 for hypoclorite read kypochlorite; column 3, line 48,for reconditioning read preconditioning; column 4, line 20, forperferably read'preferably; column 7, line 30, for silocofluoride readsilicofluorz'de; column 12, line 2, for amndable read amenable; column17, line 48, for Varp read Warp; column 19, line 70, for tetxile readtezvtz'le; and that the said Letters Patent should be read as correctedabove, so that the same may conform to the record of the case in thePatent Office.

Signed and sealed this 10th day of April, A. D. 1951.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

1. A PROCESS OF REDUCING THE SHRINKING TENDENCIES OF A WOOL-CONTAININGTEXTILE MATERIAL WHICH COMPRISES PRECONDITIONING THE SAID TEXTILEMATERIAL BY FIRST TREATING IT WITH AN ALKALINE SOLUTION OF A PEROXYCOMPOUND AND THEREAFTER REMOVING THE EXCESS ALKALINE MATERIAL,IMPREGNATING THE PRECONDITIONED TEXTILE EITH AN IMPREGNANT COMPRISING ACURABLE, NON-CATIONIC AMINOPLAST, AND ADVANCING THE CURE OF THE SAIDAMINOPLAST IN SITU, THE AMOUNT OF CURED AMINOPLAST IN THE SAID TEXTILEMATERIAL BEING SUFFICIENT TO RENDER IT RESISTANT TO SHRINKING.